Aba block copolymers for hair styling composition

ABSTRACT

A hair care composition comprising i) a polymer comprising an ABA block copolymer, wherein the A groups are poly(aminoalkylmethacrylate) blocks and the B group is derived from an ethylenically unsaturated carboxylate and, ii) a cosmetically acceptable diluent or carrier.

FIELD OF THE INVENTION

The present invention relates to hair care compositions comprising polymers, and to their use in the treatment of hair.

BACKGROUND AND PRIOR ART

Hair styling sprays, mousses, gels, shampoos and conditioners frequently contain resins, gums and adhesive polymers to provide a variety of benefits, for example, film-forming ability, thickening, sensory properties and hair shaping and setting.

It is known that compositions containing certain known hair styling polymers can perform poorly under conditions of high humidity. Thus, hair styled with these compositions can lose its shape and any other benefits conferred by the compositions when the ambient humidity increases or the hair and/or the scalp becomes damp.

Furthermore there are many sensory negatives associated with conventional polymers as they have tendency to give a sticky feel when applied to the hair, they can make the hair feel stiff and they can leave deposits.

Polymers for use in cosmetic and personal care compositions, such as for styling hair, are usually linear or graft homo- or or co-polymers which contain various monomers in an alternating, random manner.

The hydrophobic/hydrophilic character of modern styling resins is carefully balanced to produce materials that are soluble in hydroalcoholic solvents, typically 80% VOC (volatile organics content).

Block copolymers have an advantage over conventional polymers in that the polymer architecture can be controlled more readily. This is particularly important when designing polymers with segments of distinct physical and chemical properties for particular applications. WO 98/53794 discusses (AB)_(n) block copolymers, where A is a silicone block and B is a vinylic block. U.S. Pat. No. 5,271,930 (Fintex Inc) describes benzoate esters of polyalkoxylated block copolymers, such as PLURONICS™, for skin and hair care compositions. U.S. Pat. No. 5,472,686 and U.S. Pat. No. 5,660,819 (both Nippon Unicar) describe non-hydrolysing block copolymers comprising a linear polysiloxane-polyoxyalkylene block as a repeating unit in cosmetic formulations. U.S. Pat. No. 5,965,115 and U.S. Pat. No. 5,972,356 (both Procter & Gamble) describe the use of silicone-polyoxyalkylene copolymer surfactants for improving stability of a polyorganosilicone emulsion in personal care compositions.

It is an object of the present invention to provide polymers which may be used in cosmetic and personal care compositions, such as hair styling compositions, which exhibit advantages over the compositions of the prior art. In particular, the invention aims to provide a class of polymers for use in hair styling compositions. It is a further aim of the present invention to provide cosmetic and personal care compositions (e.g., hair styling compositions) which have relatively good solubility properties (eg, in water, an alcohol such as ethanol or another cosmetically acceptable solvent) and perform surprisingly well under conditions of high humidity without the sensory negatives mentioned above.

SUMMARY OF THE INVENTION

In a first aspect, the present invention provides a personal care composition comprising a polymer comprising an ABA block copolymer, wherein the A groups are polylaminoalkyl methacrylate) blocks and the B group is derived from an ethylenically unsaturated carboxylate together with a cosmetically acceptable diluent or carrier.

In another aspect, the present invention provides a cosmetic method of treating hair which comprises applying to the hair a composition according to the invention.

A further aspect of the invention is the use of a composition of the invention for the cosmetic treatment of hair.

DETAILED DESCRIPTION OF THE INVENTION

ABA Block Copolymers

The polymers of the invention may simply be ABA block copolymers or they may comprise the ABA block copolymers, with further modification such as, for example, by grafting onto the ABA block copolymer or by further reaction of the ABA block copolymer.

The polymers of the invention are preferably soluble in a solvent selected from water, ethanol and mixtures thereof. Typically, the polymers are soluble in these solvents at a level of at least 1% by weight, more preferably at least 5% by weight, most preferably at least 10 % by weight, at 25° C.

A blocks may be bonded directly to B blocks, where the chemistry of the A and B blocks permits this. Alternatively, the A blocks may be bonded to the B blocks via a suitable linker group L, so that the ABA block copolymer is of the formula A-L-B-L-A or, where the B block is branched or hyper branched, B(-L-A)_(n). Polymers of formula A-L-B-L-A and B(-L-A)_(n) fall within the meaning of the term ABA block copolymer, as used herein. Typically, L is a divalent group having a molecular weight of from 14 to 200 Daltons which links the A and B blocks, preferably via O—C, N—C or S—C bonds to the B block. Preferably L is selected from: —R—C(O)—O—; —R—O—C(O)—O—; —R—C(O)—N(R′)—; —R—O—C(O)—N(R′)—; or —R—N(R′)—C(O)—N(R″)—;

in which R is a divalent, optionally substituted, linear or branched C₁-C₁₈ hydrocarbon radical (such as C₁-C₁₂ alkylene), and

R′ and R″ are independently selected from monovalent, optionally substituted, linear or branched C₁₋₁₈ hydrocarbon radicals e.g., C₁-C₁₈ alkyl, such as methyl.

Preferably, the divalent linker group is a carbonylalkylene group containing from 2 to 7 carbon atoms which forms an ester linkage to the B block, such as, for example, a group of formula —C(O)—C(CH₃)₂—.

Examples of monovalent, unsubstituted radicals are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl and tert-pentyl radical; alkoxy radicals, such as the methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy and tert-pentoxy radicals; hexyl radicals, such as the n-hexyl radical; alkenyl radicals, such as the vinyl, allyl, 5-hexenyl, 4-vinylcyclohexyl and the 3-norbornenyl radical; cycloalkyl radicals, such as cyclopentyl, cyclohexyl, 4-ethylcyclohexyl and cycloheptyl radical; norbornyl radicals and methylcyclohexyl radicals; aryl radicals, such as the phenyl, biphenylyl, napthyl, anthryl and phenanthryl radical; alkaryl radicals, such as o-, m- and p-tolyl radical, xylyl radicals and ethylphenyl radical; and aralkyl radicals, such as the benzyl, styryl, and phenylethyl radicals.

Examples of monovalent, substituted radicals are halogenated hydrocarbon radicals, such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,4,3,3-heptafluoropentyl radical and the chlorophenyl, dichlorophenyl and trifluorotolyl radical; mercaptoalkyl radicals, such as the 2-mercaptoethyl and 3-mercaptopropyl radical; cyanoalkyl radicals, such as the 2-cyanoethyl and 3-cyanopropyl radical; aminoalkyl radicals, such as the 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl and N-(2-aminoethyl)-3-amino-(2-methyl)propyl radical; aminoaryl radicals, such as the aminophenyl radical; acyloxyalkyl radicals, such as the 3-acryloxypropyl and 3-methacryloxypropyl radical; and hydroxyalkyl radicals, such as the hydroxypropyl radical.

Preferred monovalent radicals are independently selected from unsubstituted or substituted C₁ to C₆ alkyl radicals or optionally substituted phenyl radicals, in particular methyl, ethyl, propyl or phenyl radicals.

Examples of divalent hydrocarbon radicals are linear or branched saturated alkylene radicals, such as the methylene and ethylene radical, as well as propylene, butylene, pentylene, hexylene, cyclohexylene and octadecylene radicals; alkoxyalkylene radicals such as the methoxyethylene and ethoxyethylene radical; unsaturated alkylene or arylene radicals, such as the hexenylene radical and phenylene radicals; alkarylene radicals such as the methylphenylene and ethylphenylene radical, and alkoxyarylene radicals such as the methoxyphenylene and ethoxyphenylene radical. The divalent hydrocarbon radical R can be interrupted by divalent radicals, bonded to carbon atoms on both sides, such as —O—, —C(O)O—, —O(O)C—, —CONR⁶—, —NR⁶C(O)— and —C(O)—, where R⁶ is hydrogen or a monovalent, optionally substituted, linear or branched C₁₋₁₈ hydrocarbon radical as described above.

It is preferable if in the molecular weight M_(n) of the total polymer is from 1,000 to 1,000,000, more preferably 5,000 to 500,000.

The A Blocks

The A blocks in the copolymers of the invention are of a polymer that is derived from an ethylenically unsaturated polymerisable monomer.

By “polymerisable” is meant monomers that can be polymerised by reaction between the monomers to form an extended polymer chain which is typically linear.

By “ethylenically unsaturated” is meant monomers that contain at least one polymerisable carbon-carbon double bond (which can be mono-, di-, tri- or tetra-substituted). Either a single monomer or a combination of two or more monomers can be utilised. In either case, the monomers are selected to meet the physical and chemical requirements of the final ABA block copolymer.

The A blocks, which may be the same or different in each ABA block copolymer (but which are preferably the same) preferably have a molecular weight M_(n) in the range of from 100 to 200,000 more preferably from 1,000 to 100,000, most preferably 1,000 to 20,000.

The A groups are poly(aminoalkylmethacrylate) blocks, such as, for example, poly(2-(dimethylamino)ethyl methacrylate) blocks.

The B Block

The B block of the polymer is derived from an ethylenically unsaturated carboxylate groups,

The B block is preferably represented by the formula: X—[—CH₂—CY(OR)—]_(m)—[—CY′(OR)—CH₂—]_(n)—X′

wherein m and n are integers independently greater than 1; Y and Y′ are independently H or —CH₃; R represents a hydrocarbyl group; and X and X′ independently represent substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process.

R may be selected from the group consisting of: CH₃C(O)—, Y″—C(O)—, PhC(O)—, Ph-, PhCH₂—CH₃—(CH₂—CH₂—CH₂—CH₂—), ′C(O)—, CH₃—(CH₂—CH═CH—CH₂—)eC(O)— and substituted phenyl; wherein Y″ is an n-alkyl group having up to 18 carbon atoms, Ph is phenyl, z′ is an integer up to 5000, z″ is an integer up to 5000 and the substituted phenyl is substituted with at least one substituent selected from the group consisting of NO₂,OMe, CN, NMe₂,OH, CL, Br, and F. Preferably, R is CH₃C(O)—, that is that the b block is derived from vinyl acetate.

The X and X groups preferably have homolytically cleavable CI and/or Br bonds.

Preferably, X and X are independently selected from the group consisting of BrCH2C(0)0-; BrC(Me)2C(0)0-.

BrCH2C(O)OCH2CH2NHC(O)CMe2-; and

BrCMe2C(O)OCH2CH2NHC(O)CMe2-.

wherein Me represents CH3-.

The B block, preferably have a molecular weight M_(n) in the range of from 100 to 300,000 more preferably from 1,000 to 200,000, most preferably 1,000 to 30,000.

Process for Producing ABA Block Copolymers

The polymers of the present invention may be formed by a number of different routes. However, the polymers are preferably formed according to the process described in WO 01/07496 (BP Chemicals Limited)

Particularly preferred polymers of the invention are:

DC17: Total M_(n)=28 000

-   -   where M is such that M_(n) of PVAc=8 700     -   where n and p are such that M_(n) of each block of PDMAEMA=9 700     -   PD=1.34

DC20: Total M_(n)=17 400

-   -   where M is such that M_(n) of PVAc=8 700     -   where n and p are such that M_(n) of each block of     -   PDMAEMA=4 350     -   PD=1.45     -   M_(n)=Number average molecular weight obtained by Gel Permeation         Chromatography using polystyrene standards.     -   PD=Polydispersity     -   DC 18=Quaternised DC17     -   DC21=Quaternised DC20

COMPOSITIONS OF THE INVENTION

Cosmetic or personal care compositions of the present invention are preferably formulated into hair care compositions, especially hairspray compositions, but can also be formulated into a wide variety of product types, including mousses, gels, lotions, tonics, sprays, shampoos, conditioners, rinses, hand and body lotions, facial moisturisers, sunscreens, anti-acne preparations, topical analgesics, mascaras, and the like. Compositions of the invention comprise a cosmetically acceptable diluent or carrier. Preferably, the compositions are for use in styling human hair and, more preferably, they are packaged and labelled as such.

Compositions of the invention preferably contain the polymer in an amount of from 0.01% to 30% (more preferably from 0.1 to 10%) by weight. Compositions of the invention may, optionally, comprise a fragrance or perfume and/or one or more of the optional additional components described hereinafter.

The carriers and additional components required to formulate such products vary with product type and can be routinely chosen by one skilled in the art. The following is a description of some of these carriers and additional components.

Carriers

Cosmetic or personal care compositions of the present invention can comprise a carrier, or a mixture of such carriers, which are suitable for application to the hair. The carriers are present at from about 0.5% to about 99.5%, preferably from about 5.0% to about 99.5%, more preferably from about 10.0% to about 98.0%, by weight of the composition. As used herein, the phrase “suitable for application to hair” means that the carrier does not damage or negatively affect the aesthetics of hair or cause irritation to the underlying skin.

Carriers suitable for use with hair care compositions of the present invention include, for example, those used in the formulation of hair sprays, mousses, tonics, gels, shampoos, conditioners, and rinses. The choice of appropriate carrier will also depend on the particular polymer to be used, and whether the product formulated is meant to be left on the surface to which it is applied (e.g., hair spray, mousse, tonic, or gel) or rinsed off after use (e.g., shampoo, conditioner, rinse).

The carriers used herein can include a wide range of components conventionally used in hair care compositions. The carriers can contain a solvent to dissolve or disperse the particular polymer being used, with water, the C₁-C₆ alcohols, lower alkyl acetate and mixtures thereof being preferred. The carriers can also contain a wide variety of additional materials such as acetone, hydrocarbons (such as isobutane, hexane, decene), halogenated hydrocarbons (such as Freons) and volatile silicones such as cyclomethicone.

When the hair care composition is a hair spray, tonic, gel, or mousse the preferred solvents include water, ethanol, volatile silicone derivatives, and mixtures thereof. The solvents used in such mixtures may be miscible or immiscible with each other. Mousses and aerosol hair sprays can also utilise any of the conventional propellants to deliver the material as a foam (in the case of a mousse) or as a fine, uniform spray (in the case of an aerosol hair spray). Examples of suitable propellants include materials such as trichlorofluoromethane, dichlorodifluoromethane, difluoroethane, dimethylether, propane, n-butane or isobutane. A tonic or hair spray product having a low viscosity may also utilise an emulsifying agent. Examples of suitable emulsifying agents include nonionic, cationic, anionic surfactants, or mixtures thereof. If such an emulsifying agent is used, it is preferably present at a level of from about 0.01% to about 7.5% by weight based on total weight of the composition. The level of propellant can be adjusted as desired but is generally from about 3% to about 30% by weight based on total weight for mousse compositions and from about 15% to about 50% by weight based on total weight for aerosol hair spray compositions.

Suitable spray containers are well known in the art and include conventional, non-aerosol pump sprays i.e., “atomisers”, aerosol containers or cans having a propellant, as described above, and also pump aerosol containers utilising compressed air as the propellant.

Where the hair care compositions are conditioners and rinses, the carrier can include a wide variety of conditioning materials. Where the hair care compositions are shampoos, the carrier can include, for example, surfactants, suspending agents, and thickeners. Hair styling creams or gels also typically contain a structurant or thickener, typically in an amount of from 0.01% to 10% by weight.

The carrier can be in a wide variety of forms. For example, emulsion carriers, including oil-in-water, water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone emulsions, are useful herein. These emulsions can cover a broad range of viscosities, e.g., from about 100 cps to about 200,000 cps. These emulsions can also be delivered in the form of sprays using either mechanical pump containers or pressurised aerosol containers using conventional propellants. These carriers can also be delivered in the form of a mousse. Other suitable topical carriers include anhydrous liquid solvents such as oils, alcohols, and silicones (e.g., mineral oil, ethanol, isopropanol, dimethicone, cyclomethicone, and the like); aqueous-based single phase liquid solvents (e.g., hydro-alcoholic solvent systems); and thickened versions of these anhydrous and aqueous-based single phase solvents (e.g., where the viscosity of the solvent has been increased to form a solid or semi-solid by the addition of appropriate gums, resins, waxes, polymers, salts, and the like).

Additional Components

A wide variety of additional components can be employed in compositions according to the present invention. Examples include the following:

-   -   hair styling polymers for hair styling compositions such as hair         sprays, gels, and mousses. Hair styling polymers are well known         articles of commerce and many such polymers are available         commercially which contain moieties, which render the polymers         cationic, anionic, amphoteric or nonionic in nature. The         polymers may be synthetic or naturally derived.

The amount of the polymer may range from 0.5 to 10%, preferably 0.75 to 6% by weight based on total weight of the composition.

Examples of anionic hair styling polymers are:

copolymers of vinyl acetate and crotonic acid;

terpolymers of vinyl acetate, crotonic acid and a vinyl ester of an alpha-branched saturated aliphatic monocarboxylic acid such as vinyl neodecanoate;

copolymers of methyl vinyl ether and maleic anhydride (molar ratio about 1:1) wherein such copolymers are 50% esterified with a saturated alcohol containing from 1 to 4 carbon atoms such as ethanol or butanol;

acrylic copolymers containing acrylic acid or methacrylic acid as the anionic radical-containing moiety with other monomers such as: esters of acrylic or methacrylic acid with one or more saturated alcohols having from 1 to 22 carbon atoms (such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, t-butyl acrylate, t-butyl methacrylate, n-butyl methacrylate, n-hexyl acrylate, n-octyl acrylate, lauryl methacrylate and behenyl acrylate); glycols having from 1 to 6 carbon atoms (such as hydroxypropyl methacrylate and hydroxyethyl acrylate); styrene; vinyl caprolactam; vinyl acetate; acrylamide; alkyl acrylamides and methacrylamides having 1 to 8 carbon atoms in the alkyl group (such as methacrylamide, t-butyl acrylamide and n-octyl acrylamide); and other compatible unsaturated monomers.

The polymer may also contain grafted silicone, such as polydimethylsiloxane.

Specific examples of suitable anionic hair styling polymers are:

RESYN® 28-2930 available from National Starch (vinyl acetate/crotonic acid/vinyl neodecanoate copolymer);

ULTRAHOLD® 8 available from BASF (CTFA designation Acrylates/acrylamide copolymer);

the GANTREZ®ES series available from ISP corporation esterified copolymers of methyl vinyl ether and maleic anhydride).

Other suitable anionic hair styling polymers include carboxylated polyurethanes. Carboxylated polyurethane resins are linear, hydroxyl-terminated copolymers having pendant carboxyl groups. They may be ethoxylated and/or propoxylated at least at one terminal end. The carboxyl group can be a carboxylic acid group or an ester group, wherein the alkyl moiety of the ester group contains one to three carbon atoms. The carboxylated polyurethane resin can also be a copolymer of polyvinylpyrrolidone and a polyurethane, having a CTFA designation PVP/polycarbamyl polyglycol ester. Suitable carboxylated polyurethane resins are disclosed in EP-A-0619111 and U.S. Pat. No. 5,000,955. Other suitable hydrophilic polyurethanes are disclosed in U.S. Pat. Nos. 3,822,238; 4,156,066; 4,156,067; 4,255,550; and 4,743,673.

Amphoteric hair styling polymers which can contain cationic groups derived from monomers such as t-butyl aminoethyl methacrylate as well as carboxyl groups derived from monomers such as acrylic acid or methacrylic acid can also be used in the present invention. One specific example of an amphoteric hair styling polymer is Amphomer® (Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer) sold by the National Starch and Chemical Corporation.

Examples of nonionic hair styling polymers are homopolymers of N-vinylpyrrolidone and copolymers of N-vinylpyrrolidone with compatible nonionic monomers such as vinyl acetate. Nonionic polymers containing N-vinylpyrrolidone in various weight average molecular weights are available commercially from ISP Corporation—specific examples of such materials are homopolymers of N-vinylpyrrolidone having an average molecular weight of about 630,000 sold under the name PVP K-90 and are homopolymers of N-vinylpyrrolidone having an average molecular weight of about 1,000,000 sold under the name of PVP K-120.

Other suitable nonionic hair styling polymers are cross-linked silicone resins or gums. Specific examples include rigid silicone polymers such as those described in EP-A-0240350 and cross-linked silicone gums such as those described in WO 96/31188.

Examples of cationic hair styling polymers are copolymers of amino-functional acrylate monomers such as lower alkyl aminoalkyl acrylate, or methacrylate monomers such as dimethylaminoethyl methacrylate, with compatible monomers such as N-vinylpyrrolidone, vinyl caprolactam, alkyl methacrylates (such as methyl methacrylate and ethyl methacrylate) and alkyl acrylates (such as ethyl acrylate and n-butyl acrylate).

Specific examples of suitable cationic polymers are:

copolymers of N-vinylpyrrolidone and dimethylaminoethyl methacrylate, available from ISP Corporation as Copolymer 845, Copolymer 937 and Copolymer 958;

copolymers of N-vinylpyrrolidone and dimethylaminopropylacrylamide or methacrylamide, available from ISP Corporation as Styleze® CC10;

copolymers of N-vinylpyrrolidine and dimethylaminoethyl methacrylate;

copolymers of vinylcaprolactam, N-vinylpyrrolidone and dimethylaminoethylmethacrylate;

Polyquaternium-4 (a copolymer of diallyldimonium chloride and hydroxyethylcellulose);

Polyquaternium-11 (formed by the reaction of diethyl sulphate and a copolymer of vinyl pyrrolidone and dimethyl aminoethylmethacrylate), available from ISP as Gafquat® 734, 755 and 755N, and from BASF as Luviquat® PQ11;

Polyquaternium-16 (formed from methylvinylimidazolium chloride and vinylpyrrolidone), available from BASF as Luviquat® FC 370, FC 550, FC 905 and HM-552;

Polyquaternium-46 (prepared by the reaction of vinylcaprolactam and vinylpyrrolidone with methylvinylimidazolium methosulphate), available from BASF as Luviquat®Hold.

Examples of suitable naturally-derived polymers include shellac, alginates, gelatins, pectins, cellulose derivatives and chitosan or salts and derivatives thereof. Commercially available examples include Kytamer® (ex Amerchol) and Amaze® (ex National Starch).

Also suitable for use as optional components in the compositions of the invention are the ionic copolymers described in WO 93/03703, the polysiloxane-grafted polymers disclosed in WO 93/23446, the silicone-containing polycarboxylic acid copolymers described in WO 95/00106 or WO 95/32703, the thermoplastic elastomeric copolymers described in WO 95/01383, WO 95/06078, WO 95/06079 and WO 95/01384, the silicone grafted adhesive polymers disclosed in WO 95/04518 or WO 95/05800, the silicone macro-grafted copolymers taught in WO 96/21417, the silicone macromers of WO 96/32918, the adhesive polymers of WO 98/48770 or WO 98/48771 or WO 98/48772 or WO 98/48776, the graft polymers of WO 98/51261 and the grafted copolymers described in WO 98/51755.

With certain of the above-described polymers it may be necessary to neutralise some acidic groups to promote solubility/dispersibility. Examples of suitable neutralising agents include 2-amino-2-methyl-1,3-propanediol (AMPD); 2-amino-2-ethyl-1,3-propanediol (AEPD); 2-amino-2-methyl-1-propanol (AMP); 2-amino-1-butanol (AB); monoethanolamine (MEA); diethanolamine (DEA); triethanolamine (TEA); monoisopropanolamine (MIPA); diisopropanol-amine (DIPA); triisopropanolamine (TIPA); and dimethyl stearamine (DMS). A long chain amine neutralising agent such as stearamidopropyl dimethylamine or lauramidopropyl dimethylamine may be employed, as is described in U.S. Pat. No. 4,874,604. Also suitable are inorganic neutralisers, examples of which include sodium hydroxide, potassium hydroxide and borax. Mixtures of any of the above neutralising agents may be used. Amounts of the neutralising agents will range from about 0.001 to about 10% by weight of the total composition.

-   -   sunscreening agents such as 2-ethylhexyl p-methoxycinnamate,         2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid,         2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone,         homomenthyl salicylate, octyl salicylate,         4,4′-methoxy-t-butyldibenzoylmethane, 4-isopropyl         dibenzoylmethane, 3-benzylidene camphor,         3-(4-methylbenzylidene)camphor, titanium dioxide, zinc oxide,         silica, iron oxide, and mixtures thereof.     -   anti-dandruff actives such as zinc pyrithione, piroctone         olamine, selenium disulphide, sulphur, coal tar, and the like.     -   hair conditioning agents such as hydrocarbons, silicone fluids,         and cationic materials. The hydrocarbons can be either straight         or branched chain and can contain from about 10 to about 16,         preferably from about 12 to about 16 carbon atoms. Examples of         suitable hydrocarbons are decane, dodecane, tetradecane,         tridecane, and mixtures thereof. Examples of suitable silicone         conditioning agents useful herein can include either cyclic or         linear polydimethylsiloxanes, phenyl and alkyl phenyl silicones,         and silicone copolyols. Cationic conditioning agents useful         herein can include quaternary ammonium salts or the salts of         fatty amines.     -   surfactants for hair shampoo and conditioner compositions. For a         shampoo, the level is preferably from about 10% to about 30%,         preferably from 12% to about 25%, by weight based on total         weight of the composition. For conditioners, the preferred level         of surfactant is from about 0.2% to about 3%, by weight based on         total weight of the composition. Surfactants useful in         compositions of the present invention include anionic, nonionic,         cationic, zwitterionic and amphoteric surfactants.     -   carboxylic acid polymer thickeners for hair shampoo and         conditioner compositions. These crosslinked polymers contain one         or more monomers derived from acrylic acid, substituted acrylic         acids, and salts and esters of these acrylic acids and the         substituted acrylic acids, wherein the crosslinking agent         contains two or more carbon-carbon double bonds and derived from         a polyhydric alcohol. Examples of carboxylic acid polymer         thickeners useful herein are those selected from the group         consisting of carbomers, acrylates/C10-C30 alkyl acrylate         crosspolymers, and mixtures thereof. Compositions of the present         invention can comprise from about 0.025% to about 1%, more         preferably from about 0.05% to about 0.75% and most preferably         from about 0.10% to about 0.50% of the carboxylic acid polymer         thickeners, by weight based on total weight of the composition.     -   emulsifiers for emulsifying the various carrier components of         the compositions of the invention. Suitable emulsifier types         include polyethylene glycol 20 sorbitan monolaurate (Polysorbate         20), polyethylene glycol 5 soya sterol, Steareth-20,         Ceteareth-20, PPG-2 methyl glucose ether distearate, Ceteth-10,         Polysorbate 80, cetyl phosphate, potassium cetyl phosphate,         diethanolamine cetyl phosphate, Polysorbate 60, glyceryl         stearate, PEG-100 stearate, and mixtures thereof. The         emulsifiers can be used individually or as a mixture of two or         more and can comprise from about 0.1% to about 10%, more         preferably from about 1% to about 7%, and most prefer-ably from         about 1% to about 5%, by weight based on total weight of the         composition.     -   vitamins and derivatives thereof (e.g., ascorbic acid, vitamin         E, tocopheryl acetate, retinoic acid, retinol, retinoids, and         the like).     -   cationic polymers (e.g., cationic guar gum derivatives such as         guar hydroxypropyltrimonium chloride and hydroxypropyl guar         hydroxypropyltrimonium chloride, available as the Jaguar® series         from Rhone-Poulenc).     -   preservatives, antioxidants, chelators and sequestrants; and         aesthetic components such as fragrances, colourings, hair         nutrients and essential oils.

The invention also involves a method of styling hair by applying thereto a styling composition as is hereinabove described.

The following non-limiting Examples further illustrate the preferred embodiments of the invention. All percentages referred to are by weight based on total weight unless otherwise indicated.

EXAMPLES

Bond Strength Analysis

1 μl of the 3% solids formulations were prepared using the ABA block copolymers of the invention (as described above as preferred materials) pipetted onto a hair junction. The following bond strengths were obtained. Diastron MTT600 parameters: % extension = 100 Rate (mm/min) =  10 Max force(g) = 200 Gauge force(gmf) =  2 Temperature = 25° C. Ave Bond Strength Ave Bond Strength (g) (g) at 60% RH at 80% RH DC17 36.6 +/− 7.0 28.0 +/− 4.0 DC18 10.2 +/− 3.3  5.4 +/− 2.2 DC20 38.7 +/− 5.8 32.9 +/− 4.1 DC21  8.0 +/− 3.1  8.6 +/− 2.3

The non-quaternised version of the polymer gave superior bond strength data than the quaternised version.

Examples 1,2 and Comparative Example A

The following pump spray compositions were prepared: Example 1 Example 2 Example A Polymer DC17 3 Polymer DC20 3 SCJ polymer 3 ethanol 55 55 55 water 42 42 42 Polymer DC17 and polymer DC20 as described above. SCJ polymer is a commercially available styling polymer - poly (ethyl-methacrylate-co-methacrylic acid-co-butylacrylate)

The compositions were tested by washing a wig twice with commercially available shampoo. The wig's hair is placed in velcro rollers and dried under a hood dryer for 20 minutes to set the style. The rollers are carefully removed and the initial style photographed A shield was placed over over half of the wig and the remaining half was treated with the Example by pumping the composition from a pump spray for 6 pumps. The shield was placed over the treated side of the wig and the second half of the wig was treated with a second Example in an identical manner. Photographs are taken throughout the study. The style retention is monitored by the stylist over a 30 minute time period under a controlled environment using the Sanyo Gallenkamp Chamber. Conditions 21-22° C./34-35% Humidity Treated Head A Head B Attribute Example 2 Example A Hold 3 9 Softest 12 0 Stickiest 2 10 Deposits 2 10 Flexible 10 2 Natural Movement 12 0

Conditions 25-27° C./41-46% Humidity Treated Head A Head B Attribute Example 1 Example A Hold 6 6 Softest 10 2 Stickiest 7 5 Deposits 3 9 Flexible 9 3 Natural Movement 9 3

Examples 3 to 8

The following are examples of compositions according to the invention.

The materials used in the examples include the following: Material Supplier Function Silicone emulsion X2 1787 ™ Dow Corning conditioning VOLPO CS 50 ™ Croda surfactant Chemicals Sepicide LD ™ Seppic preservative Cremophor RH410 ™ BASF stabiliser Silicone DC 200/DC 24 S ™ Dow Corning conditioning Silwet L7602/L-720 ™ Union Carbide surfactant CAP 40 ™ Calor Gas propellant Carbopol 980 ™ BF Goodrich structurant Jaguar HP-105 ™ Rhodia conditioning Silicone Fluid 245 ™ Dow Corning conditioning

Ethanol is SD Alcohol 40-B (92% active)

Example 3

A styling mousse is formulated as follows: Material % in product (w/w) Silicone Emulsion X2 1787 1.2 Polymer of any of Examples 1 to 2 1.5 VOLPO CS 50 0.3 Sepicide LD 0.4 Cremophor RH410 0.2 Ethanol 7.5 CAP 40 8.0 Perfume 0.2 Water to 100%

Example 4

A hairspray is formulated as follows: Material % in product (w/w) Polymer of any of Examples 1 to 2 3.0 Silicone DC200 0.09 Silwet L7602 0.09 CAP 40 35.0 Ethanol 60.0 Perfume 0.10 Water to 100%

Example 5

A pump spray is formulated as follows: Material % w/w Ethanol 60.0 Polymer of any of Examples 1 to 2 3.5 Silwet L-720 0.3 Silicone DC24S 0.15 Fragrance 0.3 Water to 100%

Example 6

A styling gel is formulated as follows: Material % w/w Polymer of any of Examples 1 to 2 3.8 Carbopol 980 0.4 Water to 100% Sepicide LD 0.4 Sodium hydroxide (8% 2M) 0.1 Ethanol 10.0 Cremaphor RH410 0.4 Jaguar HP-105 0.2 Perfume 0.15

Example 7

A 55% voc propelled aerosol composition is formulated as follows: Material % w/w Polymer of any of Examples 1 to 2 3.75 Silicone Fluid 245 0.20 Fragrance 0.32 Ethanol 19.53 Dimethyl ether 35.00 Sodium benzoate 0.26 Cyclohexylamine 0.21 Water to 100%

Example 8

A 55% voc pump hairspray composition is formulated as follows: Material % w/w Polymer of any of Examples 1 to 2 3.75 Cyclopentasiloxane (99% active) 0.15 Benzophenone 4 0.0001 Fragrance 0.25 Ethanol 58.00 Water to 100% 

1. A hair care composition comprising (i) a polymer comprising an ABA block copolymer, wherein the A groups are poly(aminoalkylmethacrylate) blocks built up and the B group is derived from an ethylenically unsaturated carboxylate and, (ii) a cosmetically acceptable diluent or carrier.
 2. A personal care composition as claimed in claim 1, wherein the A groups of the polymer are poly(2-(dimethylamino)ethyl methacrylate) blocks.
 3. Personal care composition according to claim 1 wherein the B group of the polymer is derived from vinylacetate.
 4. A personal care composition according to claim 1 in which the molecular weight M_(n) of the total polymer is from 5,000 to 500,000.
 5. A personal care composition according to claim 1 in which the molecular weight M_(n) of each A block of the polymer is from 1,000 to 100,000.
 6. A personal care composition according to claim 1 in which the molecular weight M_(n) of each B block of the polymer is from 1,000 to 200,000.
 7. A personal care composition as claimed in claim 1 wherein the polymer is soluble in a solvent selected from water, ethanol and mixtures thereof.
 8. A personal care composition as claimed in claim 1, further comprising a fragrance or perfume.
 9. Composition as claimed in claim 1 which is a hair styling composition.
 10. Composition as claimed in claim 1 which comprises from 0.1 to 10% by weight of the polymer.
 11. Composition as claimed in claim 1 which comprises from 0.1 to 10% by weight of the polymer.
 12. Composition as claimed in claim 1, further comprising from 0.01% to 7.5% by weight of a surfactant.
 13. Composition as claimed in claim 1, further comprising up to 30% by weight of a propellant.
 14. Composition as claimed in claim 1 which is a hair styling cream or gel including from 0.01% to 10% by weight of a structurant or thickener.
 15. A cosmetic method of treating hair which comprises applying to the hair a composition according to claim
 1. 16. Use of a composition according to claim 1 for the cosmetic treatment of hair. 